US4755283A - Fluid catalytic cracking of heavy hydrocarbon oil - Google Patents
Fluid catalytic cracking of heavy hydrocarbon oil Download PDFInfo
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- US4755283A US4755283A US06/938,450 US93845086A US4755283A US 4755283 A US4755283 A US 4755283A US 93845086 A US93845086 A US 93845086A US 4755283 A US4755283 A US 4755283A
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- heavy hydrocarbon
- surface area
- pores
- residual fraction
- hydrocarbon oil
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 238000004231 fluid catalytic cracking Methods 0.000 title description 15
- 239000011148 porous material Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 7
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 239000011238 particulate composite Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 description 35
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 239000000571 coke Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- -1 boria Chemical compound 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
Definitions
- This invention relates to a method for the conversion of a heavy hydrocarbon oil into a light hydrocarbon oil using a fluid catalytic cracking technique.
- FCC fluid catalytic cracking
- the heavy hydrocarbon oils contain a large amount of metals such as vanadium, nickel, iron and copper and carbon residue which cause the deactivation of the catalyst, resulting in the reduction of the yield of valuable fractions such as gasoline and light cycle oil and the increase of the yield of dry gas fractions such as hydrogen and C 2 lighter hydrocarbons and coke.
- an object of the present invention to provide a method of converting a heavy hydrocarbon oil into a light hydrocarbon oil using an FCC technique without encountering the problems of the conventional method.
- a method of cracking a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538° C. or higher comprising contacting the heavy hydrocarbon oil with a fluidized bed of a particulate composite catalyst which includes an amorphous refractory inorganic oxide and a crystalline aluminosilicate dispersed in said oxide and which has a surface area distribution such that the surface area of pores having pore diameters in the range of from three times to six times the average molucular size of said residual fraction is at least 60% of the surface area of pores having pore diameters in the range of 15-150 ⁇ .
- a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538° C. or higher is subjected to a fluid catalytic cracking treatment using a specific catalyst having a pore diameter distribution suitably controlled according to the average molecular size of the residual fraction.
- the catalytic conversion in the present invention is considered to proceed as follows.
- the macromolecules of the residual fraction are first cracked at acidic active sites on the amorphous refractory inorganic oxide of the catalyst to the extent that the cracked molecules can diffuse into the pores of the zeolite crystals.
- the cracked products are then further cracked within the zeolite crystals to yield gasoline and light cycle oil.
- a distillate feed stock is contacted with the catalyst at a temperature of 475°-530° C. in a reactor. Under such a reaction condition, most of the distillate is vaporized.
- the vaporized reactants whose molecular sizes are smaller than the pore diameters (7-8 ⁇ ) of the zeolite crystals, can be freely diffused through the pores of the catalyst and can diffuse into the zeolite crystals.
- the reactants which have diffused into the zeolite crystals are catalytically cracked to form mainly gasoline and light cycle oil.
- the residual fraction when the above FCC technique is applied as such to the treatment of a heavy hydrocarbon oil containing a residual fraction, the residual fraction cannot be vaporized but remains present in a liquid state. Therefore, the residual fraction cannot be freely diffused into the pores of the catalyst. Moreover, since the molecular size of the residual fraction is greater than 10 ⁇ , the molecules cannot diffuse into the zeolite crystals. As a consequence, the residual fraction is subjected to conditions as if thermally cracked in the absence of a catalyst rather than catalytically cracked, so that the formation of coke and dry gas fractions is accelerated.
- the catalyst used in the method of the present invention is a composite catalyst composed of crystalline aluminosilicate (zeolite) dispersed, generally homogeneously, in a matrix of amorphous refractory inorganic oxide. Any aluminosilicate generally used in the conventional FCC method may be suitably used in the present invention.
- the refractory inorganic oxide forming the matrix of the catalyst there may be mentioned any conventional refractory materials, such as gamma-alumina, alpha-alumina, silica, magnesia, boria, zirconia, phosphia, chromia, titania, silica-alumina, alumina-boria, alumia-phosphia and silica-magnesia.
- the content of the crystalline aluminosilicate in the catalyst is generally 5-50% by weight, preferably 15-35% by weight.
- the composite catalyst may be prepared by any known method such as described in U.S. Pat. No. 3,425,956.
- the composite catalyst should have a specific pore characteristics determined in connection with the average molecular size of the residual fraction contained in the heavy hydrocarbon oil. That is, it is essential that the surface area of pores of the catalyst having a range of pore diameters D expressed by the equation (1):
- D represents the pore diameter range ( ⁇ ) and M represents the average molecular size ( ⁇ ) of the residual fraction with a boiling point of 538° C. or higher, should be at least 60% , preferably at least 65% of the surface area of pores having pore diameters of 15-150 ⁇ in order to achieve the object of the present invention.
- the residual fraction can be relatively easily diffused into the pores having a pore diameter range of D, i.e. pore diameters in the range of from three times to six times the average molecular size of the residual fraction, and can efficiently undergo catalytic cracking.
- Pores of the catalyst which have pore diameters smaller than 3M tend to inhibit the diffusion of the residual fraction thereinto and tend to be plugged with the residual fraction.
- the catalytic cracking of the residual fraction fails to effectively proceed but, rather, the residual fraction is subjected to non-catalytic thermal cracking to form coke and dry gas fractions. Further, the light fraction with a boiling point of below 538° C. and cracked products are prevented from diffusing into the pores of the zeolite crystals.
- pores having pore diameters greater than 6M are poor in catalytic activity in cracking the residual fraction due to the decrease of surface area.
- the residual fraction tends to undergo non-catalytic thermal cracking, forming coke and dry gas fractions in a large amount.
- the particulate composite catalyst used in the method of the present invention generally has a pore volume of 0.07 ml/g or more, preferably 0.08-0.21 ml/g in pores having pore diameters of 15-150 ⁇ and a surface area of 50 m 2 /g, preferably 60-110 m 2 /g in pores having pore diameters of 15-150 ⁇ .
- the particle diameter of the composite catalyst may be that of the conventional FCC catalyst and is generally in the range of 10-150 ⁇ m.
- the heavy hydrocarbon oils to be cracked in accordance with the method of the present invention and containing a residual fraction with a boiling point of 538° C. or higher may be, for example, residual oils such as atmospheric distillation residues, vacuum distillation residues and mixtures thereof, and mixtures of the residual oils and vacuum distillate oils such as vacuum gas oils.
- the content of the residual fraction with a boiling point of 538° C. or higher in the heavy hydrocarbon oil is generally at least 5% by weight, preferably 10-70 % by weight.
- the residual fraction generally has an average molecular size of 10 ⁇ or more.
- the fluid catalytic cracking in the method of the present invention is generally performed at a temperature of 450°-550° C., preferably 480°-535° C., a pressure of 0-3 kg/cm 2 G, preferably 0.5-2 kg/cm 2 G and a weight hourly space velocity of 10-300 hour -1 , preferably 70-120 hour -1 . Details of fluid catalytic cracking are described, for instance, in Hydrocarbon Processing vol. 51, No. 9 (1972).
- pore diameter pore diameter
- surface area pore distribution
- pore distribution pore distribution
- Catalysts (A)-(D) Two kinds of heavy hydrocarbon oils (I) and (II) having the properties shown in Table 1 were subjected to thermal cracking with the use of Catalysts (A)-(D) having the compositions and properties shown in Table 2.
- Catalyst (A) is a conventional zeolite catalyst, while Catalysts (B)-(D) are composite catalysts containing zeolite dispersed in amorphous silica-alumina matrix.
- Catalysts (A)-(D) were treated with steam at 780° C. for controlling their pore structures.
- surface area is the surface area of pores having pore diameters of 15-150 ⁇ and is measured by the BET method.
- A represents the amount of a fraction in the feed stock having a boiling point of 221° C. or more and B represents the amount of a fraction in the product oil having a boiling point of 221° C. or more (except coke).
- Experiments Nos. 2 and 5 give gasoline and light cycle oil with a higher yield while reducing the production of coke as compared with the other experiments. It will be appreciated from the comparison between the results of Experiment Nos. 2 and 4 that even when the catalyst used is otherwise the same, i.e. Catalyst (B), the results are significantly inferior in the case of treatment of a feed stock whose residual fraction with a boiling point of at least 538° C. or higher has such an average molecular size that the surface area SA D of pores having a pore diameter range of D is less than 60% of the surface area SA T of pores having pore diameters in the range of 15-150 ⁇ .
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method of cracking a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538 DEG C. or higher, including contacting the heavy hydrocarbon oil with a fluidized bed of a particulate composite catalyst which includes an amorphous refractory inorganic oxide and a crystalline aluminosilicate dispersed in the oxide and which has a surface area distribution such that the surface area of pores having pore diameters in the range of from three times to six times the average molucular size of the residual fraction is at least 60% of the surface area of pores having pore diameters in the range of 15-150 ANGSTROM .
Description
This invention relates to a method for the conversion of a heavy hydrocarbon oil into a light hydrocarbon oil using a fluid catalytic cracking technique.
While there are increasing demands for light hydrocarbons, petroleum crude produced is now becoming heavier and heavier. In this circumstance, the establishment of effective techniques for converting heavy hydrocarbon oils into light hydrocarbon oils is strongly desired.
There is known a fluid catalytic cracking (FCC) method which has been developed for the production of light hydrocarbon oils such as gasoline and light cycle oil from heavy distillates such as gas oil and vacuum gas oil. The FCC method, in which a zeolite catalyst such as refractory inorganic oxide composited with crystalline aluminosilicate (zeolite) is generally used as the catalyst, has not been adopted for the conversion of heavy hydrocarbon oils containing a residual fraction with a boiling point of 538° C. or higher. This is because the heavy hydrocarbon oils contain a large amount of metals such as vanadium, nickel, iron and copper and carbon residue which cause the deactivation of the catalyst, resulting in the reduction of the yield of valuable fractions such as gasoline and light cycle oil and the increase of the yield of dry gas fractions such as hydrogen and C2 lighter hydrocarbons and coke.
It is, therefore, an object of the present invention to provide a method of converting a heavy hydrocarbon oil into a light hydrocarbon oil using an FCC technique without encountering the problems of the conventional method.
It is a special object of the present invention to provide an FCC method which can produce valuable fractions such as gasoline and light cycle oil with a high yield from heavy hydrocarbon oils.
In accordance with the present invention there is provided a method of cracking a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538° C. or higher, said method comprising contacting the heavy hydrocarbon oil with a fluidized bed of a particulate composite catalyst which includes an amorphous refractory inorganic oxide and a crystalline aluminosilicate dispersed in said oxide and which has a surface area distribution such that the surface area of pores having pore diameters in the range of from three times to six times the average molucular size of said residual fraction is at least 60% of the surface area of pores having pore diameters in the range of 15-150 Å.
In the method according to the present invention, a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538° C. or higher is subjected to a fluid catalytic cracking treatment using a specific catalyst having a pore diameter distribution suitably controlled according to the average molecular size of the residual fraction. By this, the production of coke and invaluable gaseous components may be minimized while improving the yield of valuable components such as gasoline and intermediate fractions.
The catalytic conversion in the present invention is considered to proceed as follows. The macromolecules of the residual fraction are first cracked at acidic active sites on the amorphous refractory inorganic oxide of the catalyst to the extent that the cracked molecules can diffuse into the pores of the zeolite crystals. Thus, the cracked products are then further cracked within the zeolite crystals to yield gasoline and light cycle oil.
In the conventional FCC technique using a zeolite catalyst, a distillate feed stock is contacted with the catalyst at a temperature of 475°-530° C. in a reactor. Under such a reaction condition, most of the distillate is vaporized. The vaporized reactants, whose molecular sizes are smaller than the pore diameters (7-8 Å) of the zeolite crystals, can be freely diffused through the pores of the catalyst and can diffuse into the zeolite crystals. The reactants which have diffused into the zeolite crystals are catalytically cracked to form mainly gasoline and light cycle oil. On the other hand, when the above FCC technique is applied as such to the treatment of a heavy hydrocarbon oil containing a residual fraction, the residual fraction cannot be vaporized but remains present in a liquid state. Therefore, the residual fraction cannot be freely diffused into the pores of the catalyst. Moreover, since the molecular size of the residual fraction is greater than 10 Å, the molecules cannot diffuse into the zeolite crystals. As a consequence, the residual fraction is subjected to conditions as if thermally cracked in the absence of a catalyst rather than catalytically cracked, so that the formation of coke and dry gas fractions is accelerated.
Other objects, features and advantages of the present invention will become apparent from the detailed description of the invention to follow.
The catalyst used in the method of the present invention is a composite catalyst composed of crystalline aluminosilicate (zeolite) dispersed, generally homogeneously, in a matrix of amorphous refractory inorganic oxide. Any aluminosilicate generally used in the conventional FCC method may be suitably used in the present invention. As the refractory inorganic oxide forming the matrix of the catalyst, there may be mentioned any conventional refractory materials, such as gamma-alumina, alpha-alumina, silica, magnesia, boria, zirconia, phosphia, chromia, titania, silica-alumina, alumina-boria, alumia-phosphia and silica-magnesia. The content of the crystalline aluminosilicate in the catalyst is generally 5-50% by weight, preferably 15-35% by weight. The composite catalyst may be prepared by any known method such as described in U.S. Pat. No. 3,425,956.
The composite catalyst should have a specific pore characteristics determined in connection with the average molecular size of the residual fraction contained in the heavy hydrocarbon oil. That is, it is essential that the surface area of pores of the catalyst having a range of pore diameters D expressed by the equation (1):
3M≦D≦6M (1)
wherein D represents the pore diameter range (Å) and M represents the average molecular size (Å) of the residual fraction with a boiling point of 538° C. or higher, should be at least 60% , preferably at least 65% of the surface area of pores having pore diameters of 15-150 Å in order to achieve the object of the present invention.
It has been found that the residual fraction can be relatively easily diffused into the pores having a pore diameter range of D, i.e. pore diameters in the range of from three times to six times the average molecular size of the residual fraction, and can efficiently undergo catalytic cracking. Pores of the catalyst which have pore diameters smaller than 3M tend to inhibit the diffusion of the residual fraction thereinto and tend to be plugged with the residual fraction. As a result, the catalytic cracking of the residual fraction fails to effectively proceed but, rather, the residual fraction is subjected to non-catalytic thermal cracking to form coke and dry gas fractions. Further, the light fraction with a boiling point of below 538° C. and cracked products are prevented from diffusing into the pores of the zeolite crystals. On the other hand, pores having pore diameters greater than 6M are poor in catalytic activity in cracking the residual fraction due to the decrease of surface area. As a result, the residual fraction tends to undergo non-catalytic thermal cracking, forming coke and dry gas fractions in a large amount.
The particulate composite catalyst used in the method of the present invention generally has a pore volume of 0.07 ml/g or more, preferably 0.08-0.21 ml/g in pores having pore diameters of 15-150 Å and a surface area of 50 m2 /g, preferably 60-110 m2 /g in pores having pore diameters of 15-150 Å. The particle diameter of the composite catalyst may be that of the conventional FCC catalyst and is generally in the range of 10-150 μm.
The heavy hydrocarbon oils to be cracked in accordance with the method of the present invention and containing a residual fraction with a boiling point of 538° C. or higher may be, for example, residual oils such as atmospheric distillation residues, vacuum distillation residues and mixtures thereof, and mixtures of the residual oils and vacuum distillate oils such as vacuum gas oils. The content of the residual fraction with a boiling point of 538° C. or higher in the heavy hydrocarbon oil is generally at least 5% by weight, preferably 10-70 % by weight. The residual fraction generally has an average molecular size of 10 Å or more.
The fluid catalytic cracking in the method of the present invention is generally performed at a temperature of 450°-550° C., preferably 480°-535° C., a pressure of 0-3 kg/cm2 G, preferably 0.5-2 kg/cm2 G and a weight hourly space velocity of 10-300 hour-1, preferably 70-120 hour-1. Details of fluid catalytic cracking are described, for instance, in Hydrocarbon Processing vol. 51, No. 9 (1972).
The terms "pore diameter", "surface area" and "pore distribution" used in the present specification are intended to refer to those measured by the nitrogen adsorption method (BET method). The "average molecular size" of the residual fraction having a boiling point of 538° C. or higher and contained in the heavy hydrocarbon oil may be calculated on the basis of the average moclecular structure elucidated from the results of measurement of 1 H-NMR, average molecular weight and elementary analysis. The details are described in The Journal of Japan Petroleum Society 24, No. 3, 151-159, (1981).
The following examples will further illustrate the present invention.
Two kinds of heavy hydrocarbon oils (I) and (II) having the properties shown in Table 1 were subjected to thermal cracking with the use of Catalysts (A)-(D) having the compositions and properties shown in Table 2. Catalyst (A) is a conventional zeolite catalyst, while Catalysts (B)-(D) are composite catalysts containing zeolite dispersed in amorphous silica-alumina matrix. Catalysts (A)-(D) were treated with steam at 780° C. for controlling their pore structures.
TABLE 1
______________________________________
Properties of Feed Stock
Feed Stock (I)
Feed Stock (II)
______________________________________
343-538° C. Fraction (wt %)
37.5 75.0
538° C. + Fraction (wt %)
62.5 25.0
Properties of 538° C. + fraction
Specific gravity (d15/4° C.)
0.945 1.02
Sulfur content (wt %)
0.3 4.8
Conradson carbon 3.2 6.3
residue (wt %)
Average molecular weight
590 964
Average molecular size (Å)
10 16
______________________________________
TABLE 2
______________________________________
Composition and Properties of Catalysts
Catalyst (A) (B) (C) (D)
______________________________________
Composition (wt %)
Al.sub.2 O.sub.3
33.6 45.7 46.9 46.3
Na.sub.2 O 0.8 0.3 0.3 0.3
MgO 0.5 0.6 0.9 0.6
Fe 0.2 0.1 0.1 0.1
SiO.sub.2 balance balance balance
balance
Properties
Surface area 92.7 86.2 86.4 86.6
(m.sup.2 /g)
Apparent bulk density
0.74 0.76 0.81 0.79
(g/cc)
______________________________________
In Table 2, "surface area" is the surface area of pores having pore diameters of 15-150 Å and is measured by the BET method.
The cracking test was performed at a temperature of 500° C. and with a catalyst to oil ratio of 8.0 (wt/wt) using a fluid catalytic cracking pilot test unit. The results were as summarized in Table 3, in which "pore diameter range D" is as defined by the equation (1) shown above and "conversion" is as defined as follows:
Conversion (wt %)=(B×100)/A
where A represents the amount of a fraction in the feed stock having a boiling point of 221° C. or more and B represents the amount of a fraction in the product oil having a boiling point of 221° C. or more (except coke).
As is evident from the results shown in Table 3, Experiments Nos. 2 and 5 according to the present invention give gasoline and light cycle oil with a higher yield while reducing the production of coke as compared with the other experiments. It will be appreciated from the comparison between the results of Experiment Nos. 2 and 4 that even when the catalyst used is otherwise the same, i.e. Catalyst (B), the results are significantly inferior in the case of treatment of a feed stock whose residual fraction with a boiling point of at least 538° C. or higher has such an average molecular size that the surface area SAD of pores having a pore diameter range of D is less than 60% of the surface area SAT of pores having pore diameters in the range of 15-150 Å.
TABLE 3
__________________________________________________________________________
Experiment No.
1* 2 3* 4* 5 6*
__________________________________________________________________________
Feed stock (I) (I) (I) (II)
(II)
(II)
Average molecular size
10 10 10 16 16 16
of residual fraction (Å)
Catalyst (A) (B) (C) (B) (D) (A)
Pore diameter range D (Å)
30-60
30-60
30-60
48-96
48-96
48-96
Surface area 17 61 37 37 37 11
distribution S (%)**
Results of Cracking
Conversion (wt %)
76.9
75.9
76.6
77.2
77.2
69.3
Yield (wt %)
Gas (C4--) 19.8
15.5
16.4
20.2
17.2
22.0
Gasoline (C5-221° C.)
44.7
51.3
47.8
43.5
50.7
35.2
Light cycle oil
10.8
15.5
13.7
8.7
12.6
8.5
(221-343° C.)
Heavy cycle oil
12.3
8.6
9.7
14.1
10.2
22.2
(above 343° C.)
Coke 12.4
9.1
12.4
13.5
9.3
12.1
__________________________________________________________________________
*Comparative example
**S = (SA.sub.D × 100)/SA.sub.T where SA.sub.D respresents the
surface area of pores with pore diameters D and SA.sub.T represents the
surface area of pores with pore diameters in the range of 15-150
Claims (5)
1. A method of cracking a heavy hydrocarbon oil containing a residual fraction with a boiling point of 538° C. or higher, said method comprising contacting the heavy hydrocarbon oil with a fluidized bed of a particulate composite catalyst which includes an amorphous refractory inorganic oxide and a crystalline aluminosilicate dispersed in said oxide, said crystalline aluminosilicate having a surface area distribution such that the surface area of pores having pore diameters in the range of from three times to six times the average molecular size of said residual fraction is at least 60% of the surface area of pores having pore diameters in the range of 15-150 Å.
2. A method as claimed in claim 1, wherein the content of said residual fraction in the heavy hydrocarbon oil is at least 5% by weight.
3. A method as claimed in claim 1, wherein said particulate catalyst has a pore volume of at least 0.07 ml/g in pores with pore diameters of 15-150 Å and a surface area of at least 50 m2 /g in pores with pore diameters of 15-150 Å.
4. A method as claimed in claim 1, wherein said contact is at a temperature of 450°-550° C., a pressure of 0-3 kg/cm2 G and a weight hourly space velocity of 10-300 hour-1.
5. The method of claim 1 wherein the content of said residual fraction in the heavy hydrocarbon oil is 10-70% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/938,450 US4755283A (en) | 1986-12-05 | 1986-12-05 | Fluid catalytic cracking of heavy hydrocarbon oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/938,450 US4755283A (en) | 1986-12-05 | 1986-12-05 | Fluid catalytic cracking of heavy hydrocarbon oil |
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| Publication Number | Publication Date |
|---|---|
| US4755283A true US4755283A (en) | 1988-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| US06/938,450 Expired - Fee Related US4755283A (en) | 1986-12-05 | 1986-12-05 | Fluid catalytic cracking of heavy hydrocarbon oil |
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| US (1) | US4755283A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999024164A1 (en) * | 1997-11-11 | 1999-05-20 | Solvay (Societe Anonyme) | Process for producing spherical catalyst particles, catalyst particles and their use in a chemical synthesis |
| US5961817A (en) * | 1996-10-15 | 1999-10-05 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite |
| US6022471A (en) * | 1996-10-15 | 2000-02-08 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite and rare earth oxide |
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| US3425956A (en) * | 1964-03-26 | 1969-02-04 | Grace W R & Co | Process for preparing molecular sieve containing cracking catalysts |
| US3912619A (en) * | 1972-08-21 | 1975-10-14 | Grace W R & Co | Preparation of cracking catalyst |
| US3944482A (en) * | 1973-08-08 | 1976-03-16 | Gulf Research & Development Company | Process for the cracking of high metals content feedstocks |
| US4217240A (en) * | 1976-09-02 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stable aluminosilicate aquasols having uniform size particles and their preparation |
| US4257874A (en) * | 1977-08-31 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Petroleum refinery processes using catalyst of aluminosilicate sols and powders |
| US4310441A (en) * | 1977-02-16 | 1982-01-12 | Filtrol Corporation | Large pore silica-alumina gels and method of producing the same |
| US4362651A (en) * | 1979-03-22 | 1982-12-07 | Schwarzenbek Eugene F | High porosity catalysts |
| US4457833A (en) * | 1981-08-27 | 1984-07-03 | Ashland Oil, Inc. | Process and catalyst for the conversion of carbo-metallic containing oils |
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|---|---|---|---|---|
| US3425956A (en) * | 1964-03-26 | 1969-02-04 | Grace W R & Co | Process for preparing molecular sieve containing cracking catalysts |
| US3912619A (en) * | 1972-08-21 | 1975-10-14 | Grace W R & Co | Preparation of cracking catalyst |
| US3944482A (en) * | 1973-08-08 | 1976-03-16 | Gulf Research & Development Company | Process for the cracking of high metals content feedstocks |
| US4217240A (en) * | 1976-09-02 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stable aluminosilicate aquasols having uniform size particles and their preparation |
| US4310441A (en) * | 1977-02-16 | 1982-01-12 | Filtrol Corporation | Large pore silica-alumina gels and method of producing the same |
| US4257874A (en) * | 1977-08-31 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Petroleum refinery processes using catalyst of aluminosilicate sols and powders |
| US4362651A (en) * | 1979-03-22 | 1982-12-07 | Schwarzenbek Eugene F | High porosity catalysts |
| US4457833A (en) * | 1981-08-27 | 1984-07-03 | Ashland Oil, Inc. | Process and catalyst for the conversion of carbo-metallic containing oils |
| US4624773A (en) * | 1983-08-16 | 1986-11-25 | Ashland Oil, Inc. | Large pore catalysts for heavy hydrocarbon conversion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5961817A (en) * | 1996-10-15 | 1999-10-05 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite |
| US6022471A (en) * | 1996-10-15 | 2000-02-08 | Exxon Research And Engineering Company | Mesoporous FCC catalyst formulated with gibbsite and rare earth oxide |
| WO1999024164A1 (en) * | 1997-11-11 | 1999-05-20 | Solvay (Societe Anonyme) | Process for producing spherical catalyst particles, catalyst particles and their use in a chemical synthesis |
| US6465382B1 (en) | 1997-11-11 | 2002-10-15 | Solvay (Societe Anonyme) | Process for producing spherical catalyst particles, catalyst particles and their use in a chemical synthesis |
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